Process for the production of chlorinated alkanes

ABSTRACT

Processes for the production of chlorinated alkanes are provided. The present processes comprise catalyzing the chlorination of a feedstream comprising one or more alkanes and/or alkenes with a catalyst system comprising one or more inorganic iodine salts and/or lower than conventional levels of elemental iodine and at least one Lewis acid. The processes are conducted in a nonaqueous media, and so, the one or more inorganic iodine salts are recoverable and/or reusable, in whole or in part.

This application is a 371 of PCT/US2012/067268, filed Nov. 30, 2012,which claims benefit of 61/566,213, filed Dec. 2, 2011.

The present invention relates to processes for the production ofchlorinated alkanes in a nonaqueous media.

BACKGROUND

Hydrofluorocarbon (HFC) products are widely utilized in manyapplications, including refrigeration, air conditioning, foam expansion,and as propellants for aerosol products including medical aerosoldevices. Although HFC's have proven to be more climate friendly than thechlorofluorocarbon and hydrochlorofluorocarbon products that theyreplaced, it has now been discovered that they exhibit an appreciableglobal warming potential (GWP).

The search for more acceptable alternatives to current fluorocarbonproducts has led to the emergence of hydrofluoro-olefin (HFO) products.Relative to their predecessors, HFOs are expected to exert less impacton the atmosphere in the form of a lesser, or no, detrimental impact onthe ozone layer and their lower GWP as compared to HFC's.Advantageously, HFO's also exhibit low flammability and low toxicity.

As the environmental, and thus, economic importance of HFO's hasdeveloped, so has the demand for precursors utilized in theirproduction. Many desirable HFO compounds, e.g., such as2,3,3,3-tetrafluoroprop-1-ene or 1,3,3,3-tetrafluoroprop-1-ene, maytypically be produced utilizing feedstocks of chlorocarbons, and inparticular, highly chlorinated alkanes, e.g., tetra- andpentachloroalkanes.

Unfortunately, these higher chlorides have proven difficult tomanufacture using acceptable process conditions and in commerciallyacceptable regioselectivities and yields. For example, conventionalprocesses for the production of pentachloropropanes provide unacceptableselectivity to the desired pentachloropropane isomer(s), i.e.,1,1,2,2,3-pentachloropropane, make use of suboptimal chlorinatingagents, require the use of high intensity process conditions and/orcatalyst systems that are difficult to utilize in large scale productionprocesses and/or are wholly or partly unrecoverable or otherwiseunreusable.

It would thus be desirable to provide improved processes for theproduction of chlorocarbon precursors useful as feedstocks in thesynthesis of refrigerants and other commercial products. Moreparticularly, such processes would provide an improvement over thecurrent state of the art if they provided a higher regioselectivityrelative to conventional methods, made use of optimal chlorinatingagents, required low intensity process conditions, made use of catalystsystems and/or initiators more amenable to use in large-scale processes,such as those that may be recovered or otherwise reused.

BRIEF DESCRIPTION

The present invention provides efficient processes for the production ofhighly chlorinated alkanes. More particularly, the processes make use ofone or more inorganic iodine salts, or other inorganic precursors to atleast one hypervalent iodine species, and/or low levels of elementaliodine desirably as part of a mixed catalyst system further comprisingat least one Lewis acid. The use of inorganic iodine salts isadvantageous as compared to conventional processes, in that inorganiciodine salts are not as corrosive or volatile as elemental iodine whenemployed at conventional levels, and so, are more readily andconveniently incorporated into large scale manufacturing process.Because the present processes are desirably conducted in a nonaqueousmedia, the inorganic iodine salts are recoverable and/or reusable,providing significant cost savings to the process. Further cost savingsare provided in that low intensity process conditions, e.g., lowtemperatures, ambient pressure and minimal reactor residence time, areutilized.

In one aspect, the present invention provides a process for theproduction of chlorinated alkanes. The process comprises catalyzing thechlorination of a feedstream comprising one or more alkanes and/oralkenes in a nonaqueous media with a mixed catalyst system comprisingone or more inorganic iodine salts, and/or less than 10,000 ppmelemental iodine and at least one Lewis acid. Although an inorganiciodine salt is used as part of the catalyst system, and in someadvantageous embodiments, no iodine is added to the starting alkaneand/or alkene. In some embodiments, the one or more inorganic iodinesalts may comprise hypoiodites (IO⁻), iodites (IO²⁻), iodates IO³⁻,and/or periodates (IO⁴⁻), including metaperiodates and orthoperiodates,or combinations of these. In some embodiments, the concentration ofelemental iodine used, if any, may be from 1 ppm to 5000 ppm, or from 5ppm to 1000 ppm, or from 10 ppm to 100 ppm. The source of chlorine atomsmay comprise chlorine gas, sulfuryl chloride or a combination of these,and in some embodiments comprises sulfuryl chloride, which may also actas a diluent or solvent as well as a chlorine source. The alkane and/oralkene may initially be unchlorinated, or, may already comprise chlorineatoms, and may comprise any number of carbon atoms.

DETAILED DESCRIPTION

The present specification provides certain definitions and methods tobetter define the present invention and to guide those of ordinary skillin the art in the practice of the present invention. Provision, or lackof the provision, of a definition for a particular term or phrase is notmeant to imply any particular importance, or lack thereof. Rather, andunless otherwise noted, terms are to be understood according toconventional usage by those of ordinary skill in the relevant art.

The terms “first”, “second”, and the like, as used herein do not denoteany order, quantity, or importance, but rather are used to distinguishone element from another. Also, the terms “a” and “an” do not denote alimitation of quantity, but rather denote the presence of at least oneof the referenced item, and the terms “front”, “back”, “bottom”, and/or“top”, unless otherwise noted, are merely used for convenience ofdescription, and are not limited to any one position or spatialorientation.

If ranges are disclosed, the endpoints of all ranges directed to thesame component or property are inclusive and independently combinable(e.g., ranges of “up to 25 wt. %, or, more specifically, 5 wt. % to 20wt. %,” is inclusive of the endpoints and all intermediate values of theranges of “5 wt. % to 25 wt. %,” etc.). As used herein, percent (%)conversion is meant to indicate change in molar or mass flow of reactantin a reactor in ratio to the incoming flow, while percent (%)selectivity means the change in molar flow rate of product in a reactorin ratio to the change of molar flow rate of a reactant.

Reference throughout the specification to “one embodiment” or “anembodiment” means that a particular feature, structure, orcharacteristic described in connection with an embodiment is included inat least one embodiment. Thus, the appearance of the phrases “in oneembodiment” or “in an embodiment” in various places throughout thespecification is not necessarily referring to the same embodiment.Further, the particular features, structures or characteristics may becombined in any suitable manner in one or more embodiments.

As used herein, the term “inorganic iodine salt” is meant to include anyinorganic salt, incorporating, or otherwise capable of providing orforming in a reaction mixture, at least one hypervalent iodine species.Typically, such compounds may further be characterized in that theycomprise at least metal and iodine elements. The term “hypervalent”, inturn, refers to iodine sources having oxidation states of greater thanor equal to +1, e.g., +1, +3, +5, +7, etc.

The present invention provides efficient processes for the production ofchlorinated alkanes. The present processes catalyze the chlorination ofa feedstream comprising one or more alkanes and/or alkenes with one ormore inorganic iodine salt and at least one Lewis acid. Further, theprocesses take place in a nonaqueous media, and as a result, the one ormore inorganic iodine salts may be recovered in whole or in part, and/orreused. The use of an inorganic iodine salt is further advantageous inthat inorganic iodine salts do not present the volatility and corrosionissues that can be presented by elemental iodine when used atconventional levels, as is used in conventional processes for theproduction of chlorinated alkanes.

Any inorganic iodine salt can be used in the mixed catalyst system, andthose of ordinary skill in the art are expected to be familiar withmany. Suitable examples include, but are not limited to, hypoiodites(IO⁻), iodites (IO²⁻), iodates (IO³⁻), and/or periodates (IO⁴⁻),including mesoperiodates and orthoperiodates, or combinations of these.Specific examples of inorganic iodine salts include, but are not limitedto sodium iodate, silver iodate, calcium iodate, potassium iodate, iodicacid, sodium periodate, potassium periodate, barium periodate, andperiodic acid, and derivatives or combinations of any number of these.

In other embodiments, elemental iodine may be used, but at levels muchlower than previously thought to be effective. That is, it has now beendiscovered that amounts of iodine much lower than conventionallyutilized, e.g., 0.01 wt %, provide improvements in yield and selectivitywhile yet not presenting the corrosion and volatility issues that mayarise when these conventional levels are utilized. More specifically,amounts of elemental iodine of from 1 ppm to 5000 ppm, or from 5 ppm to1000 ppm, or from 10 ppm to 100 ppm, have now surprisingly beendiscovered to provide selectivities to the desired chloropropanes ofgreater than 60%, in some cases greater than 70%, and in some casesgreater than 80%. This is a significant improvement over processeswherein no iodine is used at all, wherein conversions of e.g., less than60% can be seen. Since elemental iodine can be costly, significant costsavings are also provided by using the smaller amounts described herein.Combinations of one or more inorganic iodine salts and elemental iodinemay also be used.

The mixed catalyst system used in the process also desirably comprisesat least one Lewis acid. Any Lewis acid that at least marginallyenhances the process can be utilized, and examples of these include, butare not limited to ferric chloride, antimony pentafluoride, borontrichloride, aluminum trichloride, and stannic chloride. Combinations oftwo or more of these may also be used, if desired. In some embodiments,anhydrous aluminum chloride may desirably be utilized as the at leastone Lewis acid.

Generally speaking, enough of the mixed catalyst system should beutilized to provide some improvement to reaction process conditions(e.g., a reduction in required temperature) and desirably, reactionselectivity, but yet not be more than will provide any additionalbenefit, if only for reasons of economic practicality. For purposes ofillustration only, then, it is expected that useful concentrations ofthe inorganic iodine salt, in a batch process, will range from 0.01% to30% by weight with respect to the alkane and/or alkene, or from 0.1% to20%, or from 1% to 10 wt %, inclusive of all subranges therebetween.Surprisingly low levels of elemental iodine are effective, e.g., from 1ppm to 5000 ppm, or from 5 ppm to 1000 ppm, or from 10 ppm to 100 ppm.Suitable amounts of the Lewis acid will range from 0.01% to 20% byweight each with respect to the dichlorinated alkane, or from 0.1% to10%, or from 1% to 5 wt %, inclusive of all subranges therebetween. Forcontinuous processes, it is possible that much lower concentrations,e.g., as much as 5, or 10, or 15 or even 20 times lower will not only beeffective, but be effective over the entire course of plant operability.

The chlorine atoms are desirably supplied by chlorine gas, sulfurylchloride, or both. Sulfuryl chloride (SO₂Cl₂), can also act as a solventfor the mixed catalyst systems and/or reactions, thereby assisting inthe provision of an acceptable reaction rate and/or yield. And so, insome embodiments, sulfuryl chloride may desirably be used as thechlorinating agent.

In some embodiments, including those wherein chlorine is used as achlorinating agent rather than sulfuryl chloride, a solvent may be usedin the present processes. Desirably, any solvent will be inert to thedesired chemistry, allow for adequate mass transfer during the chemicalreaction, and create a homogenous phase to insure uniform reactivitythroughout the reactor. Chlorocarbon solvents are especially well suitedfor the present processes due to their ease in handling and relativeresistance to the desired chemistry, and many of these are known tothose of ordinary skill in the art. For example, suitable chlorocarbonsolvents include, but are not limited to carbon tetrachloride, methylenechloride, chloroform, 1,2,3-trichloropropane,1,1,2,3-tetrachloropropane, and 1,1,2,2,3,3-hexachloropropane. In someembodiments, the chlorocarbon solvent may comprise methylene chloride or1,2,3-trichloropropane.

The reaction conditions under which the process is carried out areadvantageously low intensity. That is, low temperatures, e.g., of lessthan 100° C., or less than 90° C., or less than 80° C. or less than 70°C., or less than 60° C., may be utilized and the desired selectivitiesto the desired chlorinated alkanes yet be realized. In some embodiments,temperatures of from 40° C. to 90° C., or from 50° C. to 80° C., or from55° C. to 75° C. may be utilized. Similarly, ambient pressure issuitable for carrying out the process, or pressures within 250, or 200,or 150, or 100, or 50, or 40, or 30, or 20, or even 10 psi, of ambientare suitable. Reactor occupancy may also be minimized with the desiredselectivities yet seen—for example, reactor occupancy times of less than20 hours, or less than 15 hours, or less than 10 hours, or less than 9,8, 7, 6, or even 5 hours, are possible. The reactor may be any suitableliquid phase reactor, such as a batch or continuous stirred tankautoclave reactor with an internal cooling coil. A shell and multitubeexchanger followed by vapor liquid disengagement tank or vessel can alsobe used.

The present process can make use of one or more alkanes or alkenes toproduce the desired chlorinated alkanes. Alkanes or alkenes having anynumber of carbon atoms and that are desirably chlorinated in anonaqueous media may benefit from application of the present process.Generally speaking, alkanes or alkenes comprising from 2-10 carbonatoms, or from 2-8 carbon atoms, or from 2-6 carbon atoms, or from 2-5carbon atoms, or from 2-4 carbon atoms, are particularly suitable. Insome embodiments, the alkane or alkene may comprise a propane orpropene.

Similarly, the alkane and or alkene may be unchlorinated, or maycomprise chlorine atoms prior to application of the process. That is,the alkane and/or alkene may comprise any number of chlorine atoms,including zero. To some degree, the number of chlorine atoms in thealkane or alkene will be limited by the number of carbon atoms, as wellas the chlorinated alkane desirably produced. In some embodiments, thealkane and/or alkene may comprise from 0-4 chlorine atoms, or maycomprise 1-3 chlorine atoms. In some embodiments, the alkane and/oralkene may be a mono-, di-, or trichlorinated propane, such as 1- or2-chloropropane, 1,2-dichlorinated propane, and/or 1,1,2-trichlorinatedpropane.

The chlorinated alkane produced by the process will depend upon thealkane and/or alkene used as a starting material, and so, in someembodiments, and due to the commercial significance of trichlorinatedalkanes having three to six carbon atoms, the use of one or morepropanes, propenes, butanes, butenes, pentanes, pentenes, hexanes andhexanes as starting materials may be preferred.

In one exemplary process, a dichloropropane, e.g., 1,2-dichloropropane,is utilized as a starting material and reacted with sulfuryl chloride inthe presence of sodium iodate at a temperature of from 55° C. to 75° C.,ambient pressure and a reactor occupancy of less than five hours toproduce a pentachloropropane, e.g., 1,1,2,2,3-pentachloropropane atregioselectivities of greater than 10:1, or greater than 20:1 or greaterthan 30:1, or even greater than 40:1, over other pentachloropropaneproducts.

Some embodiments of the invention will now be described in detail in thefollowing examples.

EXAMPLE 1 Chlorination of 1,2-dichloropropane to1,1,2,2,3-pentachloropropane Using Sodium Periodate as Inorganic IodineSalt, Aluminum Chloride as Lewis acid and Sulfuryl Chloride asChlorinating Agent

17 g sulfuryl chloride and 2.5 g aluminum chloride is charged to areactor equipped with a magnetic stir bar and reflux condenser. Thereaction mixture is heated to 60° C. and then 4.1 g of1,2-dichloropropane is charged. The reaction is allowed to stir for 35minutes, where GC analysis indicated that >99% of the1,2-dichloropropane had been reacted to form primarily1,1,2-trichloropropane.

An additional 15 g of sulfuryl chloride along with 1 g of sodiumperiodate is added. The reaction is allowed to react for a total 4 hoursbefore being cooled back to ambient temperature. The crude reactionmixture is filtered to collect the sodium periodate catalyst as a wetcake that is washed with methylene chloride to give 0.8 g of recoveredsodium periodate.

The reaction mixture and methylene chloride wash are combined, slowlypoured into an ice water bath, and allowed to stir until quenched. Theorganic and aqueous phases are separated and the aqueous phase isextracted with an equal volume of methylene chloride. The combinedorganic fractions are dried over magnesium sulfate, the excess solventis removed by rotary evaporator, and the final product is isolated as acolored oil.

GC and NMR analysis of the final product mixture shows a yield of 4.7 gof 1,1,2,2,3-pentachloropropane, 0.7 g of tetrachloropropane isomers,0.4 g of 1,1,2-trichloropropane, 0.3 g of hexachloropropane isomers, and0.2 g of 1,2,3-trichloropropane.

EXAMPLE 2 Chlorination of 1,2-dichloropropane to1,1,2,2,3-pentachloropropane Using Recovered Sodium Periodate asInorganic Iodine Salt, Aluminum Chloride as Lewis Acid and SulfurylChloride as Chlorinating Agent

9.3 g sulfuryl chloride and 1.3 g aluminum chloride is charged to areactor equipped with a magnetic stir bar and reflux condenser. Thereaction mixture is heated to 60° C. and charged with 2.3 g of1,2-dichloropropane. The reaction is allowed to stir for 35 minutes,when GC analysis indicates that >99% of the 1,2-dichloropropane hasreacted to form primarily 1,1,2-trichloropropane.

An additional 7.9 g of sulfuryl chloride along with 0.5 g of sodiumperiodate recovered from Example 1 is charged. The reaction is allowedto react for a total 4 hours before being cooled back to ambienttemperature. The crude reaction mixture is filtered to collect thesodium periodate catalyst as a wet cake that is washed with methylenechloride to give 0.45 g of recovered sodium periodate.

The reaction mixture and methylene chloride wash are combined, slowlypoured into an ice water bath, and allowed to stir until quenched. Theorganic and aqueous phases are separated and the aqueous phase isextracted with an equal volume of methylene chloride. The combinedorganic fractions are dried over magnesium sulfate, the excess solventis removed by rotary evaporator, and the final product is isolated as acolored oil.

GC and NMR analysis of the final product mixture shows a yield of 3.1 gof 1,1,2,2,3-pentachloropropane, 0.5 g of hexachloropropane isomers, 0.1g of 1,2,3-trichloropropane, and 0.1 g of tetrachloropropane isomers.

EXAMPLE 3 Chlorination of 1,2-dichloropropane to1,1,2,2,3-pentachloropropane Using Sodium Iodate as Inorganic IodineSalt, Aluminum Chloride as Lewis acid and Sulfuryl Chloride asChlorinating Agent

17 g sulfuryl chloride and 2.5 g aluminum chloride is charged to areactor equipped with a magnetic stir bar and reflux condenser. Thereaction mixture is heated to 60° C. and then 4.1 g of1,2-dichloropropane is charged. The reaction is allowed to stir for 35minutes, when GC analysis indicates that >99% of the 1,2-dichloropropanehas reacted to form primarily 1,1,2-trichloropropane.

An additional 15 g of sulfuryl chloride along with 0.5 g of sodiumiodate is charged. The reaction is allowed to react for a total 4 hoursbefore being cooled back to ambient temperature. The reaction mixture isslowly poured into an ice water bath and allowed to stir until quenched.The organic and aqueous phases are separated and the aqueous phase isextracted with an equal volume of methylene chloride. The sodium iodateis recovered in the aqueous wash as indicated by ion chromatographyanalysis. The combined organic fractions are dried over magnesiumsulfate, the excess solvent is removed by rotary evaporator, and thefinal product was isolated as a colored oil.

GC and NMR analysis of the final product mixture shows a yield of 5.4 gof 1,1,2,2,3-pentachloropropane, 0.6 g of tetrachloropropane isomers,0.4 g of hexachloropropane isomers, 0.3 g of 1,1,2-trichloropropane and0.2 g of 1,2,3-trichloropropane.

EXAMPLE 4 Chlorination of 1,2-dichloropropane to1,1,2,2,3-pentachloropropane Using Sodium Iodate as Inorganic IodineSalt, Aluminum Chloride as Lewis Acid and Sulfuryl Chloride asChlorinating Agent

17 g sulfuryl chloride, 0.6 g aluminum chloride, and 0.8 g of sodiumiodate is charged to a reactor equipped with a magnetic stir bar andreflux condenser. The reaction mixture is heated to 60° C. and then 4.1g of 1,2-dichloropropane is added. The reaction is allowed to stir for atotal 4 hours before being cooled back to ambient temperature.

The reaction mixture is slowly poured into an ice water bath and allowedto stir until quenched. The organic and aqueous phases are separated andthe aqueous phase is extracted with an equal volume of methylenechloride. The sodium iodate is recovered in the aqueous wash asindicated by ion chromatography analysis. The combined organic fractionsare dried over magnesium sulfate, the excess solvent is removed byrotary evaporator, and the final product is isolated as a colored oil.

GC and NMR analysis of the final product mixture shows a yield of 2.3 gof 1,1,2,2,3-pentachloropropane, 1.4 g of 1,1,2-trichloropropane, 0.9 gof tetrachloropropane isomers, 0.8 g of 1,2,3-trichloropropane, and 0.2g of hexachloropropane isomers.

EXAMPLE 5 Chlorination of 1,1,2-trichloropropane to1,1,2,2,3-pentachloropropane Using Low Levels of Elemental Iodine,Aluminum Chloride as Lewis Acid, Chlorine as Chlorinating Agent, andMethylene Chloride as Chlorocarbon Solvent

A product stream is prepared by feeding chlorine gas at 30 sccm througha starting mixture of 22.6 wt % 1,2-dichloropropane, 1.3 wt % aluminumchloride, and 76.1 wt % methylene chloride at 130 psig and 70° C. untilGC analysis indicates that the starting dichloropropane has undergone68% conversion to give 1,1,2-trichloropropane as the major intermediatespecies. This stream is charged with 35 ppm elemental iodine dissolvedin 15 mL of methylene chloride based on initial dichloropropane withinthe reaction mixture. The resulting mixture is allowed to stir until36.1% conversion of the 1,1,2-trichloropropane intermediate is observedto give the desired pentachloropropane and its precursors (can weidentify these please?) in 82.3% selectivity over the undesiredbyproducts of 1,1,2,2,3,3-hexachloropropane and1,1,2,3-tetrachloropropane. When viewed in light of Example 6, thisexample shows that virtually the same conversion of1,1,2-trichloropropane with virtually the same selectivity to thedesired pentachloropropane when a significantly lower amount ofelemental iodine is used than is conventional. When viewed incombination with Example 7, this example shows that even these lowlevels of iodine result in significantly greater selectivities to thedesired pentachloropropanes than no elemental iodine at all.

EXAMPLE 6 Chlorination of 1,1,2-trichloropropane to1,1,2,2,3-pentachloropropane Using Conventional Levels of Iodine,Aluminum Chloride as Lewis Acid, Chlorine as Chlorinating Agent, andMethylene Chloride as Inert Chlorocarbon Solvent

A product stream is prepared by feeding chlorine gas at 30 sccm througha starting mixture of 22.6 wt % 1,2-dichloropropane, 1.3 wt % aluminumchloride, and 76.1 wt % methylene chloride at 130 psig and 70° C. untilGC analysis indicates that the starting dichloropropane has undergone69.7 wt % conversion to give 1,1,2-trichloropropane as the majorintermediate species. This stream is charged with 0.57 wt % elementaliodine dissolved in 15 mL of methylene chloride based on initialdichloropropane within the reaction mixture. The resulting mixture isallowed to stir until 33.0% conversion of the 1,1,2-trichloropropaneintermediate is observed to give the desired pentachloropropane and itsprecursors in 85.4% selectivity over the undesired byproducts of1,1,2,2,3,3-hexachloropropane and 1,1,2,3-tetrachloropropane.

EXAMPLE 7 Chlorination of 1,1,2-trichloropropane to1,1,2,2,3-pentachloropropane in the Absence of Elemental Iodine UsingAluminum Chloride as Lewis Acid, Chlorine as Chlorinating Agent, andMethylene Chloride as Inert Chlorocarbon Solvent

A product stream is prepared by feeding chlorine gas at 30 sccm througha starting mixture of 22.6 wt % 1,2-dichloropropane, 1.3 wt % aluminumchloride, and 76.1 wt % methylene chloride at 130 psig and 70° C. untilGC analysis indicates that the starting dichloropropane has undergone71.5 wt % conversion to give 1,1,2-trichloropropane as the majorintermediate species. This stream is charged with 15 mL of methylenechloride. The resulting mixture is allowed to stir until 28.3%conversion of the 1,1,2-trichloropropane intermediate is observed togive the desired pentachloropropane and its precursors in 53.9%selectivity over the undesired byproducts of1,1,2,2,3,3-hexachloropropane and 1,1,2,3-tetrachloropropane.

The invention claimed is:
 1. A process for the production of chlorinated propanes comprising, in a nonaqueous media, catalyzing the chlorination of a feedstream comprising one or more propanes with a mixed catalyst system comprising at least one Lewis acid selected from the group consisting of ferric chloride, antimony pentafluoride, boron trichloride, aluminum trichloride, stannic chloride or combinations of these, and one or more inorganic iodine salts, wherein the process produces one pentachloropropane at a regioselectivity of greater than 10:1 over other pentachloropropane products; and wherein the source of chlorine atoms comprises chlorine gas, sulfuryl chloride or a combination of these.
 2. The process of claim 1, wherein the Lewis acid comprises aluminum trichloride.
 3. The process of claim 1, wherein the process is conducted in the presence of a chlorocarbon solvent.
 4. The process of claim 1, wherein the propane comprises from 0-4 chlorine atoms.
 5. The process of claim 4, wherein the propane is a trichloropropane.
 6. The process of claim 1, wherein the chlorinated propane comprises from 2-6 chlorine atoms.
 7. The process of claim 6, wherein the chlorinated propane comprises a pentachloropropane.
 8. The process of claim 7, wherein the chlorinated propane comprises 1,1,2,2,3-pentachloropropane.
 9. The process of claim 1, wherein the inorganic iodine salt is recovered from the process.
 10. The process of claim 1, wherein the inorganic iodine salt comprises one or more hypoiodites, iodites, iodates, periodates, or combinations of these.
 11. The process of claim 10, wherein the inorganic iodine salt comprises sodium iodate, silver iodate, calcium iodate, potassium iodate, iodic acid, sodium periodate, potassium periodate, barium periodate, periodic acid, or derivatives or combinations of any number of these.
 12. The process of claim 11, wherein the inorganic iodine salt comprises sodium iodate, potassium iodiate, sodium periodate, or combinations of these.
 13. A process for the production of a product comprising a pentachloropropane, the process comprising treating a feedstream comprising propanes, with a Lewis acid catalyst, a chlorine source, and one or more inorganic iodine salts, in a nonaqueous solvent, wherein the Lewis acid is selected from the group consisting of ferric chloride, antimony pentafluoride, boron trichloride, aluminum trichloride, stannic chloride and a combination thereof; the chlorine source is Cl₂, SO₂Cl₂, or a mixture thereof, and the one or more inorganic iodine salts that are selected from the group consisting of sodium iodate, silver iodate, calcium iodate, potassium iodate, iodic acid, sodium periodate, potassium periodate, barium periodate, and periodic acid.
 14. A process according to claim 13, wherein the Lewis acid catalyst is aluminum trichloride, and at least one inorganic salt is sodium periodate.
 15. A process according to claim 13, wherein the nonaqueous solvent comprises methylene chloride.
 16. A process according to claim 13, wherein the pentachloropropane is 1,1,2,2,3-pentachloroprpopane.
 17. A process according to claim 13, wherein the pentachloropropane is 1,1,2,2,3-pentachloroprpopane; the Lewis acid catalyst is aluminum trichloride; at least one inorganic salt is sodium periodate; wherein the product also comprises 1,1,2,2,3,3-hexachloropropane, and the amount of 1,1,2,2,3-pentachloroprpopane prepared in grams, is greater than the amount of 1,1,2,2,3,3-hexachloropropane prepared in grams. 